WO2008065090A1 - Composition de polyuréthane chargée de métal et moules préparés à partir de celle-ci - Google Patents

Composition de polyuréthane chargée de métal et moules préparés à partir de celle-ci Download PDF

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Publication number
WO2008065090A1
WO2008065090A1 PCT/EP2007/062835 EP2007062835W WO2008065090A1 WO 2008065090 A1 WO2008065090 A1 WO 2008065090A1 EP 2007062835 W EP2007062835 W EP 2007062835W WO 2008065090 A1 WO2008065090 A1 WO 2008065090A1
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Prior art keywords
composition
polyol
mould
metal
molecular weight
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PCT/EP2007/062835
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English (en)
Inventor
Elisa Corinti
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Dow Global Technologies Inc.
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Publication date
Application filed by Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Priority to US12/516,893 priority Critical patent/US20100331472A1/en
Priority to CN2007800506685A priority patent/CN101611082B/zh
Priority to BRPI0717921-9A2A priority patent/BRPI0717921A2/pt
Publication of WO2008065090A1 publication Critical patent/WO2008065090A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/40—Plastics, e.g. foam or rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2305/00—Use of metals, their alloys or their compounds, as reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2305/00—Use of metals, their alloys or their compounds, as reinforcement
    • B29K2305/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/08—Transition metals
    • B29K2705/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/08—Transition metals
    • B29K2705/14—Noble metals, e.g. silver, gold or platinum

Definitions

  • the present invention relates to a polyurethane composition, a method of making the polyurethane composition and the use of the polyurethane composition for making moulds, particularly moulds for shoe soles.
  • Moulds for shoe soles are typically made of aluminium.
  • the problem with these moulds are that they are expensive, because aluminium is an expensive raw material, and the cost associated with a slow production time as a result of the difficulty of working with aluminium bio cks .
  • moulds made from these materials also suffer from considerable disadvantages.
  • initial shoe sole production is good, there is a rapid increase in mould temperature from 25 to 60 0 C, with soles moulded at a temperature of greater than 45°C showing problems caused by a change in the chemical reactivity of the surface of the polyurethane mould at temperatures greater than 45°C.
  • This problem could be resolved by cooling the moulds or allowing them to be cooled to less than 40 0 C.
  • this has the disadvantage of slowing down the process.
  • US6602936 discloses a composition comprising a resin containing a single polyepoxide and a polyisocyanate and a filler, which can be a metal powder.
  • the aim of the present invention to provide a new material which can be used for making moulds, particularly for shoe soles, the material being cheaper than the aluminium moulds currently used.
  • the material can be processed using the same tools as for aluminium moulds, but more easily and more quickly, but at the same time can produce soles of equivalent quality and at an equivalent rate to aluminium moulds.
  • a composition comprising a polyurethane and from 20 to 80 weight percent of a particulate metal or metal alloy filler, wherein polyurethane is the reaction product of: a) a first polyol, the first polyol having a molecular weight of less than 1000; b) a second polyol, the second polyol having a molecular weight of from 1500 to 10000; and c) at least one polyisocyanate, and wherein the particulate metal or metal alloy filler has a thermal conductivity of at least 150 watts/m.°K.
  • the metal or metal alloy can be non-ferromagnetic or ferromagnetic.
  • the metal or metal alloy is non-ferromagnetic, and more preferably at least one of aluminium, copper, zinc, gold, bronze and silver.
  • the particulate is in the form of one or more of granules, platelets, pellets, beads, flakes, particles, lamellae or grains.
  • at least one of the first and second polyols is a polyether polyol, and more preferably, both first and second polyols are polyether polyols.
  • the composition preferably additionally comprises at least one of a water absorbent, such as a zeolite; an antifoaming agent; and a viscosity cutter.
  • a water absorbent such as a zeolite
  • an antifoaming agent such as a zeolite
  • a viscosity cutter Some antifoaming agents can act as a viscosity cutter, and so an additional viscosity cutter may not be required.
  • a particularly preferred composition comprises a polyurethane, a zeolite paste and a particulate metal or metal alloy filler, wherein the polyurethane is the reaction product of: a) from 40 to 60 parts by weight of a first polyether polyol, the first polyether polyol having a molecular weight of from 100 to 600 and a functionality of from 2 to 8; b) from 40 to 60 parts by weight of a second polyether polyol, the second polyether polyol having a molecular weight of from 1500 to 8000 and a functionality of from 2 to 6; and c) at least one isocyanate, wherein the isocyanate is present in an amount to provide for an isocyanate index of from 80 to 115, and wherein the composition comprises from 5 to 15 parts by weight of the zeolite paste and from 50 to 200 parts by weight of a particulate aluminium filler.
  • the composition of the first aspect of the invention may be used to produce any solid article. However, it is particularly suitable for producing a mould, such as a mould for forming part of a footwear article, such as a shoe or a boot, and in particular for forming a sole of the footwear article.
  • a mould such as a mould for forming part of a footwear article, such as a shoe or a boot, and in particular for forming a sole of the footwear article.
  • the composition can also be used in the production of moulds for other purposes, such as for producing furniture parts and mechanical parts.
  • the mould is suitable for use where the article to be produced is a plastics material, such as polyurethane, and in particular for the production of an article in which the plastics material can be poured or injected into the mould.
  • Typical conditions for pouring the plastics material are a temperature range of from 25 to 130 0 C and a pressure of 0 to 5 bar.
  • the moulds are also suitable for use at temperatures higher than 130 0 C.
  • Polyurethane foams are commonly used to manufacture a large number of different articles.
  • One particular example is the field of sporting goods, and more particularly, shooting and archery targets, which may be in the form of animals and birds.
  • the moulds used in the production of these targets are usually very crude, and as they are typically sold very cheaply, it is not economical to use custom-made metal moulds to produce higher quality, less crude targets.
  • the compositions of the present invention are particularly suitable for use in the production of moulds, for example by using computer- aided design, which can produce targets having greater detail.
  • the moulds produced are both cheap and of high quality, which will reduce the number of rejects produced.
  • a mould for producing a plastics material part comprising a polyurethane and a particulate metal or metal alloy filler, wherein the polyurethane is the reaction product of: a) a first polyol, the first polyol having a molecular weight of less than 1000; b) a second polyol, the second polyol having a molecular weight of from 1500 to 10000; and c) at least one polyisocyanate.
  • at least one of the first and second polyols is a polyether polyol, and more preferably, both first and second polyols are polyether polyols.
  • a mould for a part of a footwear article for example a sole, formed from a composition comprising a polyurethane and at least one particular metal or metal alloy filler, wherein the polyurethane is the reaction product of at least one polyol and at least one isocyanate.
  • the polyol is a polyether polyol.
  • a large number of alternative materials could be used which have improved heat dissipation, including metal carbonates, oxides, sulphates and sulphides. However, it is not sufficient simply to improve heat dissipation; it is also necessary to ensure that the composition has the correct properties for machining into the shape of the mould, including turning, milling, shaving, holing and threading. It is important that the material does not produce excessive dust when being machined. In addition, it is important that the material is sufficiently structurally sound to ensure that a mould can be made. It is also important that the material does not have excessive thermal expansion, which would affect the shape of the mould as it gets hotter during use. Further important features are that the composition is not too dense, and has sufficient hardness.
  • a method of producing a mould comprising the steps of: i) mixing a first polyol having a molecular weight of less than 1000 and a second polyol having a molecular weight of from 1500 to 10000; ii) adding a particulate metal filler to the mixture of step i) wherein the metal has a thermal conductivity of at least 150 watts/m.°K; iii) mixing the polyol and filler mixture under vacuum; and iv) adding at least one isocyanate and mixing.
  • step iv) can be undertaken under vacuum. However, it is typically undertaken at ambient pressure.
  • at least one of the first and second polyols is a poly ether polyol, and more preferably, both first and second polyols are polyether polyols.
  • a water absorbent such as a zeolite, is additionally added in step i).
  • the surface of the mould is sufficiently smooth so that there are no defects on the surface of the resultant sole.
  • the filler and the polyol are mixed, bubbles form in the mixture which results in flaws in the mould material which are then present on the surface of the mould after machining.
  • the resultant composition has a very smooth, shiny finish.
  • the mould can be formed by any known methods. Suitable methods include pouring the reaction mixture onto a model to form the mould or milling a block to the appropriate mould shape.
  • composition of the present invention is particular useful for the production of moulds for prototype parts, where a relatively small quantity of parts (for example up to 1000) are required.
  • a mould according to the present invention can be produced more quickly and more cost effectively than the corresponding aluminium mould. This enables the producer to produce a set of identical parts for rapid evaluation, without the high cost of producing an aluminium mould, as was previously necessary.
  • the composition is also suitable for use in the production of moulds for other plastics material parts as well as prototypes.
  • a method of producing a plastics material part comprising producing the mould as described above or undertaking the method as described above, and using the mould to produce the part.
  • the part is a prototype part.
  • the composition of the present invention is non-cellular, that is the composition is not a foam.
  • the composition has a density of at least 1.2 g/cm . More preferably, the composition has a density of at least 1.3 and yet more preferably 1.45 g/cm .
  • the composition has a density of less than 2.2 g/cm 3 , more preferably less than 1.8 g/cm 3 .
  • the only polymer present is a polyurethane in the composition. It is particularly preferred that the composition does not contain any polyepoxide.
  • the metal or metal alloy particulate to be used can either be one metal or metal alloy or a mixture of metals and/or metal alloys.
  • the metal or metal alloy to be used is typically one having a high thermal conductivity. Suitable metals are ones having a thermal conductivity of at least 150 watts/m.°K. It is preferred that the metal has a thermal conductivity of at least 180, more preferably at least 200 watts/m.°K.
  • the metal or metal alloy is suitably one which is not ferro -magnetic. However, in some cases, ferromagnetic metals can be used on their own or in combination with non-ferromagnetic metals.
  • Suitable metals or metal alloys include aluminium (235 watts/m.°K), copper (400 watts/m.°K), zinc (194 watts/m.°K), bronze, gold (317 watts/m.°K) and silver (429 watts/m.°K). It is preferred that the metal is aluminium or copper or a combination thereof, and more preferably the metal is aluminium.
  • the metal filler is in the form of a particulate such that it can be spread throughout the resultant polyurethane composition during mixing of the polyol side, prior to addition of the isocyanate.
  • exemplary types of particulate include granules, platelets, pellets, beads, flakes, particles or grains.
  • the present invention can suitably be used with any type of particulate.
  • the metal or metal alloy filler is in the form of spherical or substantially spherical particulate. Fillers of this type offer the best all round characteristics. Where fillers which are platelets are used, the thermal conductivity of the resultant polymer is substantially improved.
  • the reaction mixture is very viscous and hard to mix, and therefore platelets are less favourable than spherical particulate.
  • the particulate has a mean diameter of from 20 to 100 micrometers, regardless of shape.
  • the filler consists of metal or metal alloy particles having a mean diameter of from 20 to 40 micrometers.
  • aluminium particles having a mean diameter of from 30 to 40 micrometers.
  • the metal or metal alloy filler is preferably used in an amount of from 20 to 80 weight percent, based on the total weight of the composition. It is further preferred that the metal filler is used in an amount of from 30 to 70 weight percent, and yet more preferably from 35 to 55 weight percent.
  • the compositions of the present invention are formed using a polyurethane, which is the reaction product of at least one polyol and at least one isocyanate. Although it is preferred that the polyol is a polyether polyol, a polyester polyol can be used.
  • the composition is formed using a first polyol having a molecular weight of less than 1000 (a low molecular weight polyol) and a second polyol having a molecular weight of from 1500 to 10000 (a high molecular weight polyol).
  • a first polyol having a molecular weight of less than 1000 a low molecular weight polyol
  • a second polyol having a molecular weight of from 1500 to 10000 a high molecular weight polyol.
  • the combination of two different polyols provides a polyurethane having excellent physical properties for use as a mould.
  • the low molecular weight polyol provides the hardness for the resultant composition, whilst the high molecular weight composition provides elasticity to prevent the composition being too brittle.
  • first and second polyols are polyether polyols, and more preferably, both first and second polyols are polyether polyols.
  • the low molecular weight polyether polyol preferably has a molecular weight of from 100 to 600g/mol, more preferably from 125 to 500 and most preferably from 150 to 450g/mol.
  • the low molecular weight polyether polyols include those obtained by the alkoxylation of suitable starting molecules with an alkylene oxide, such as ethylene, propylene, butylene oxide, or a mixture thereof.
  • alkylene oxide such as ethylene, propylene, butylene oxide, or a mixture thereof.
  • initiator molecules include water, ammonia, aniline or polyhydric alcohols such as dihydric alcohols, especially the alkane polyols such as ethylene glycol, propylene glycol, hexamethylene diol, glycerol, trimethylol propane or trimethylol ethane, or the low molecular weight alcohols containing ether groups such as diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol.
  • initiators include pentaerythritol, xylitol, arabitol, sorbitol, mannitol and the like. Particularly preferred is glycerin.
  • a poly(propylene oxide) polyol including poly(oxypropylene- oxyethylene) polyols, is used.
  • the oxyethylene content should comprise less than about 40 weight percent of the total and preferably less than about 25 weight percent of the total weight of the polyol.
  • the ethylene oxide can be incorporated in any manner along the polymer chain, which stated another way means that the ethylene oxide can be incorporated either in internal blocks, as terminal blocks, may be randomly distributed along the polymer chain, or may be randomly distributed in a terminal oxyethylene-oxypropylene block.
  • These polyols are conventional materials prepared by conventional methods.
  • polyether polyols include the poly(tetramethylene oxide) polyols, also known as poly(oxytetramethylene) glycol, that are commercially available as diols. These polyols are prepared from the cationic ring-opening of tetrahydrofuran and termination with water as described in Dreyfuss, P. and M. P. Dreyfuss, Adv. Chem. Series, 91, 335 (1969).
  • the low molecular weight polyol preferably has a functionality, i.e the number of isocyanate reactive hydrogens per polyol, of at least 1.5, more preferably from 2 to 8, yet more preferably from 2 to 6 and most preferably from 2 to 4.
  • the polyol preferably has a hydro xyl number of from 100 to 700 and preferably from 400 to 600.
  • a particularly preferred low molecular weight polyether polyol is Voranol® CP 260, which is available from The Dow Chemical Company. This polyol has a functionality of 3 and a molecular weight of 260g/mol.
  • the amount of low molecular weight polyol used is preferably from 5 to 95 weight percent, based on the total amount of polyol used. More preferably, from 10 to 90, yet more preferably from 15 to 85 and most preferably from 40 to 60 weight percent of low molecular weight polyol is used.
  • the high molecular weight polyether polyols include those obtained by the alkoxylation of suitable starting molecules with an alkylene oxide, such as ethylene, propylene, butylene oxide, or a mixture thereof.
  • initiator molecules include water, ammonia, aniline or polyhydric alcohols such as dihydric alcohols having a molecular weight of 62 to 399, especially the alkane polyols such as ethylene glycol, propylene glycol, hexamethylene diol, glycerol, trimethylol propane or trimethylol ethane, or the low molecular weight alcohols containing ether groups such as diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol.
  • Other commonly used initiators include pentaerythritol, xylitol, arabitol, sorbitol, mannitol and the like. Particularly preferred is glycerin.
  • a poly(propylene oxide) polyol including poly(oxypropylene- oxyethylene) polyols
  • the oxyethylene content should comprise less than about 40 weight percent of the total and preferably less than about 25 weight percent of the total weight of the polyol.
  • the ethylene oxide can be incorporated in any manner along the polymer chain, which stated another way means that the ethylene oxide can be incorporated either in internal blocks, as terminal blocks, may be randomly distributed along the polymer chain, or may be randomly distributed in a terminal oxyethylene-oxypropylene block.
  • These polyols are conventional materials prepared by conventional methods.
  • polyether polyols include the poly(tetramethylene oxide) polyols, also known as poly(oxytetramethylene) glycol, that are commercially available as diols. These polyols are prepared from the cationic ring-opening of tetrahydrofuran and termination with water as described in Dreyfuss, P. and M. P. Dreyfuss, Adv. Chem. Series, 91, 335 (1969).
  • the high molecular weight polyol preferably has a molecular weight of from 1500 to 8000, more preferably from 2000 to 7000, yet more preferably from 2500 to 6000 and most preferably from 4000 to 5000 g/mol.
  • the high molecular weight polyol preferably has a functionality of at least 1.5, more preferably from 2 to 6, yet more preferably from 2 to 4 and most preferably from 2 to 3.
  • a particularly preferred polyol is a mixed propylene oxide-ethylene oxide polyol, with an ethylene oxide endcap.
  • the polyol preferably has a hydro xyl number of from 20 to 90 and more preferably from 30 to 40.
  • a particularly preferred high molecular weight polyether polyol is Voranol® CP 4711 , which is available from The Dow Chemical Company.
  • This polyol is formed using a glycerin starter and is a mixed ethylene oxide -propylene oxide polyol having a 14% ethylene oxide endcap.
  • the polyol has a molecular weight of 4700, an OH value of 35 and a primary OH content of 70 to 75%.
  • the amount of high molecular weight polyol used is preferably from 5 to 95 weight percent, based on the total amount of polyol used. More preferably, from 10 to 90, yet more preferably from 15 to 85, even more preferably from 30 to 70 and most preferably from 40 to 60 weight percent of high molecular weight polyol is used.
  • Suitable polyester polyols which can be used instead of one or both of the polyether polyols include those produced from dicarboxylic acids, preferably aliphatic dicarboxylic acids, having 2 to 12 carbon atoms in the alkylene radical, and multifunctional alcohols, preferably diols.
  • acids include, for instance, aliphatic dicarboxylic acids such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and preferably, succinic and adipic acids; cycloaliphatic dicarboxylic acids such as 1,3- and 1 ,4-cyclohexane dicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.
  • aliphatic dicarboxylic acids such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and preferably, succinic and adipic acids
  • cycloaliphatic dicarboxylic acids such as 1,3- and 1 ,4-cyclohexane dicarboxylic acid
  • di- and multifunctional, particularly difunctional, alcohols are: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3 -propanediol, 1,10-decanediol, glycerine, trimethylolpropane, and preferably, 1 ,4-butanediol, and 1,6-hexanediol.
  • Other suitable polyester polyols would be known to the skilled person.
  • polystyrene resin can also be used in combination with the low and high molecular weight polyols. Such polyols are preferably used in an amount of less than 10 weight percent of the total polyol used. However, it is preferred that no other polyols are used.
  • Suitable polyisocyanates for use in the present invention include aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates.
  • alkylene diisocyanates having from 4 to 12 carbon atoms in the alkylene radical, for example dodecane 1,12- diisocyanate, 2-ethyltetramethylene 1,4- diisocyanate, 2- methylpentamethylene 1,5-diisocyanate, tetramethylene 1 ,4-diisocyanate and preferably hexamethylene 1,6-diisocyanate; cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1 ,4-diisocyanate and also any mixtures of these isomers, 1- isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate), hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer mixtures, dicyclohexylmethane 4,4'-, 2,2'- and 2,4 '-
  • isocyanates are modified polyfunctional isocyanates, i.e. products which are obtained by chemical reaction of organic diisocyanates and/or polyisocyanates. Examples which may be mentioned are diisocyanates and/or polyisocyanates containing ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione and/or urethane groups.
  • modified polyisocyanates which have been found to be useful are liquid polyisocyanates containing carbodiimide groups and/or isocyanurate rings and having NCO contents of from 33.6 to 15% by weight, preferably from 31 to 21% by weight, based on the total weight, for example those on the basis of diphenylmethane 4,4'-, 2,4'- and/or 2,2'- diisocyanates and/or tolylene 2, 4- and/or 2,6-diisocyanate.
  • modified polyisocyanates can, if desired, be mixed with one another or with unmodified organic polyisocyanates such as diphenylmethane 2,4'- and/or 4,41- diisocyanate, raw MDI, tolylene 2,4- and/or 2,6-diisocyanate.
  • unmodified organic polyisocyanates such as diphenylmethane 2,4'- and/or 4,41- diisocyanate, raw MDI, tolylene 2,4- and/or 2,6-diisocyanate.
  • Polyisocyanates which have been found to be particularly useful are diphenylmethane diisocyanate isomer mixtures or raw MDI having a diphenylmethane diisocyanate isomer content of from 33 to 55% by mass and polyisocyanate mixtures containing urethane groups and based on diphenylmethane diisocyanate having an NCO content of from 15 to 33% by mass.
  • a preferred isocyanate is ISONATE® M143, which is commercially available from The Dow Chemical Company.
  • ISONATE® M143 has an NCO content of 29.5 weight percent, an equivalent weight of 1.43 and a functionality of 2.15.
  • the polyisocyanate is used in an amount to provide for an isocyanate reaction index of advantageously from 80 to 130, preferably from 85 to 110, and more preferably from 90 to 105.
  • isocyanate index it is understood that at an index of 100, one equivalent of isocyanate is present for each isocyanate reactive hydrogen atom present from the polyol, or other active hydrogen atom bearing substance able to react with the polyisocyanate.
  • Additional optional components which are suitably included in the composition include additional filler, surface active agents, water absorbents, anti-foaming agents, viscosity cutters and colorants. These components are typically added to the polyol side of the reactants, prior to addition of the polyisocyanate.
  • Additional fillers can be any standard filler known to the skilled person, such as for example chalk or mica. Additional fillers, where present, are used in amounts of less that 10% and preferably less than 5% by weight, based on the total weight of the composition.
  • Suitable surface-active substances are, for example, compounds which serve to aid the homogenization of the starting materials and may also be suitable for regulating the cell structure of the plastics.
  • emulsifiers such as the sodium salts of castor oil sulphates or of fatty acids and also amine salts of fatty acids, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, e.g.
  • alkali metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid foam stabilizers such as siloxane- oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleate esters, Turkey red oil and peanut oil and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • oligomeric acrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying action, the cell structure and/or stabilizing the foam.
  • the surface -active substances are usually employed in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of polyol.
  • Any suitable water absorbents known to the skilled person can be used. However, it is preferred that the water absorbent is a zeolite.
  • the zeolite can be added in powder form or in paste form.
  • a particularly preferred zeolite paste is Voratron EG 711, produced by the Dow Chemical Company.
  • anti-foaming agents known to the skilled person can be used, including silicone and non-silicone containing anti-foaming agents. It is preferred that the anti- foaming agent is used in an amount of less than 2 percent by weight.
  • One preferred commercially available anti-foaming agent is Antifoam 1500, which is produced by Dow Corning.
  • the composition includes a viscosity cutter.
  • the anti-foaming agent acts as the viscosity cutter.
  • it is typically used in an amount of less than 2 percent by weight.
  • suitable viscosity cutters include those of BYK-Chemie, such as BYK®-W 985, BYK®-W 995 and BYK®-W 996.
  • Figure 1 is a bar chart showing the thermal conductivity of a series of polymers containing a filler
  • Figure 2 is a chart showing the surface temperature of a series of bone moulds during moulding. Examples 1 to 10
  • compositions were made using a variety of different fillers, as well as a polyurethane-only composition. All of the compositions were made using the same basic polyurethane composition as shown in Table 1 :
  • the isocyanate (Isonate 143M) was added to give an isocyanate index of between 90 and 95.
  • Example 1 the polyurethane mixture for each example was formed into a plate of dimension 20cm x 20cm by lcm and the thermal conductance of the plate was measured using a LASERCOMP FOX 200 using EN 12667. The thermal conductance was measured in the temperature range of 30 to 40 0 C. The weight percentage for each filler used, based on the total weight of the composition, and the resulting thermal conductance of the composition are given in Table 2. The thermal conductance results are shown in Figure 1. Table 2
  • Examples marked (C) are comparative examples and are not part of the present invention. They relate to compositions made with the same polyurethane, but with no filler or non-metallic fillers.
  • the composition comprising the mixture of Al powder and lamellar Al has a particularly high thermal conductance, which is higher than the powder or lamellar Al alone.
  • the use of a mixture of particulate of different shapes appears to provide a synergistic effect.
  • the metal particulate is formed of a mixture of substantial spherical particulate and lamellar particulate
  • Polyurethane moulds were formed using the compositions in Table 2 for making so called "bone” moulds, which are moulds for forming flat sheets.
  • the bone mould was formed to measure the temperature behaviour of the mould during pouring of a polyurethane formulation that is typically used for making shoe moulds.
  • Figure 2 shows the temperature measurement of the surface of the moulds after pouring of the polyurethane into the mould.
  • compositions were also formed into blocks so that the physical properties could be measured, including the suitability of the materials for processing into moulds by turning, milling, holing and threading.
  • the composition does not show significant thermal expansion.
  • the thermal expansion was measured by measuring the change in the length of the part relative to the initial length of the part over a temperature range. The shrinkage is given per degree of temperature change.
  • Other physical properties are also important, such as the density and the hardness.
  • a mould should have a density of less than 1.8 g/cm and a hardness of greater than 70 when measured by Shore D, according to ASTM D2240.
  • the composition must be sufficiently dimensionally stable such that it does not break or collapse on machining, that it has a good surface quality and that the composition does not form excessive dust on milling.
  • the production of dust is not only dangerous for the workers, but also causes problems for cleaning of the apparatus after milling.
  • Table 3 compares the results of these tests for a number of the Examples. As can be seen, the compositions of the present invention compare favourably with those which are not part of the present invention. In particular, the compositions which are not part of the invention typically demonstrate either poor thermal conductance or poor expansion, as well as often producing dust on milling. Table 3
  • Example 3 is particularly suitable for use in the production of moulds.
  • a number of the other compositions according to the present invention also produced good moulds.
  • Moulds with a particularly good surface were produced by using a vacuum when adding the filler to the polyol and also by inclusion of an anti-foaming agent.
  • the benefit of a good mould surface is that the resultant article produced from the mould has similar excellent surface properties.
  • a filled polyurethane mould according to the present invention can be produced for significantly less cost than the corresponding mould made solely from aluminium.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

Composition comprenant un polyuréthane et de 20 à 80 pour cent en poids d'une matière de charge en métal ou alliage de métal particulaire, caractérisée en ce que le polyuréthane est le produit réactionnel d'un premier polyol ayant un poids moléculaire inférieur à 1000, d'un second polyol ayant un poids moléculaire allant de 1500 à 10000 et d'au moins un polyisocyanate et caractérisée en ce que la matière de charge en métal ou alliage de métal particulaire a une conductivité thermique d'au moins 150 watts/m.°K; moule fabriqué à partir de celle-ci; et procédé de production d'un tel moule.
PCT/EP2007/062835 2006-12-01 2007-11-26 Composition de polyuréthane chargée de métal et moules préparés à partir de celle-ci WO2008065090A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US12/516,893 US20100331472A1 (en) 2006-12-01 2007-11-26 Metal filled polyurethane composition and moulds prepared therefrom
CN2007800506685A CN101611082B (zh) 2006-12-01 2007-11-26 金属填充的聚氨酯组合物以及由其制造的模具
BRPI0717921-9A2A BRPI0717921A2 (pt) 2006-12-01 2007-11-26 Composição, molde, molde para produzir uma peça de material plástico, molde para uma parte de um calçado e método para produzir um molde

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06256166.7 2006-12-01
EP06256166A EP1927621B1 (fr) 2006-12-01 2006-12-01 Composition de polyurethane chargé de métal et moules produits de celle-ci

Publications (1)

Publication Number Publication Date
WO2008065090A1 true WO2008065090A1 (fr) 2008-06-05

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US (1) US20100331472A1 (fr)
EP (1) EP1927621B1 (fr)
CN (1) CN101611082B (fr)
AT (1) ATE461966T1 (fr)
BR (1) BRPI0717921A2 (fr)
DE (1) DE602006013160D1 (fr)
PL (1) PL1927621T3 (fr)
RU (1) RU2009125041A (fr)
TW (1) TW200837143A (fr)
WO (1) WO2008065090A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2596936B1 (fr) * 2011-11-24 2015-09-09 ABB Research Ltd. Moule et procédé de production d'articles formés à partir d'une composition durcissable aux UV
DE102013002519B4 (de) 2013-02-13 2016-08-18 Adidas Ag Herstellungsverfahren für Dämpfungselemente für Sportbekleidung
DE102016209046B4 (de) 2016-05-24 2019-08-08 Adidas Ag Verfahren zur herstellung einer schuhsohle, schuhsohle, schuh und vorgefertigte tpu-gegenstände
DE102016209045B4 (de) 2016-05-24 2022-05-25 Adidas Ag Verfahren und vorrichtung zum automatischen herstellen von schuhsohlen, sohlen und schuhe
WO2017219344A1 (fr) * 2016-06-24 2017-12-28 Dow Global Technologies Llc Composite de polyuréthane métallisé et son procédé de préparation
JP6889902B2 (ja) * 2016-12-27 2021-06-18 ナミックス株式会社 樹脂組成物、硬化物、導電性膜、導電性パターン及び衣服
US20220234256A1 (en) * 2021-01-28 2022-07-28 Adidas Ag Mold and method for manufacturing a component by molding, component thereof and shoe with such a component
CN115404037B (zh) * 2022-09-29 2023-08-15 东莞市纳百川电子科技有限公司 一种金属手模焊缝填充材料、制备方法及焊缝处理工艺

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WO1993012170A1 (fr) * 1991-12-19 1993-06-24 Hans Dammer Composition de resine, notamment de resine de coulee
GB2268496A (en) * 1992-07-08 1994-01-12 Intersurgical Ltd Improved thermal capacity reticulated polymer foams
EP1101783A2 (fr) * 1999-11-22 2001-05-23 Vantico AG Résine à couler et procédé pour la préparation de moules de résine
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Also Published As

Publication number Publication date
PL1927621T3 (pl) 2010-08-31
CN101611082B (zh) 2013-05-08
RU2009125041A (ru) 2011-01-10
ATE461966T1 (de) 2010-04-15
EP1927621B1 (fr) 2010-03-24
CN101611082A (zh) 2009-12-23
TW200837143A (en) 2008-09-16
BRPI0717921A2 (pt) 2013-10-22
EP1927621A1 (fr) 2008-06-04
US20100331472A1 (en) 2010-12-30
DE602006013160D1 (de) 2010-05-06

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